Carbometallate: Komplexe Anionenverbände [MoC4/26—] in der Kristallstruktur von Pr[MoIIC2]

Carbometalates: Complex Anions equation/tex2gif-stack-4.gif [MoC_4/2^6—] in the Crystal Structure of Pr equation/tex2gif-stack-5.gif [Mo^IIC₂] Criteria for the existence of carbometalates are established and discussed in a broader context. The concept is then applied to the novel compound Pr₂[MoC₂], which is characterized by chemical analyses, X‐ray diffraction and metallography. The crystal structure (tetragonal, P4₂/mnm, Z = 4, a = 581.29(8) pm, c = 1032.53(14) pm) consists of layered polyanions equation/tex2gif-stack-6.gif[MoC_4/2^6—] of distorted vertex and edge sharing MoC₄ tetrahedra. Praseodymium is also in a distorted tetrahedral coordination by carbon. The physical properties show “bad metal” behaviour and localized magnetic 4f‐moments in agreement with the existence of Pr³⁺‐species. A detailed bonding analysis using both the electron localization function ELF and the COHP method justifies the interpretation of the title compound as a carbomolybdate(II).     

Excited states in 163,164Ho populated through incomplete-fusion reactions

High-spin states in ^163,164Ho were investigated by means of in-beam -ray spectroscopy techniques using the multidetector array GASP. Excited states in ^163,164Ho were populated predominantly through the incomplete-fusion mechanism in the ¹⁶⁰Gd (¹¹B reaction at a beam energy of 61 MeV. Known rotational bands in ¹⁶³ Ho have been extended to higher spins and a three-quasiparticle band has been observed in this nucleus. Rotational bands have been identified in ¹⁶⁴Ho and their configurations have been discussed. Empirical Gallagher-Moszkowski (GM) splitting energies were extracted from the and GM doublets. Alignments, band crossing frequencies, and electromagnetic properties have been analyzed in the framework of the cranking model.Received: 13 February 2004, Revised: 18 March 2004, Published online: 14 September 2004PACS: 21.10.Re Collective levels - 21.60.Ev Collective models - 23.20.Lv transitions and level energies - 27.70. + q      

A dipole band in 124Xe

High-spin states in ¹²⁴Xe were populated by means of the ¹¹⁰Pd(¹⁸O,4n) reaction. In-beam γ rays were measured using the GASP spectrometer. A dipole band, similar to those previously found in other nuclei of this mass region, was identified in ¹²⁴Xe.     

Measurement and analysis of the ν2 and ν4 infrared bands of 13CD4

A Fourier transform infrared spectrum of 91% ¹³CD₄ has been recorded between 885 and 1193 cm^?1 with a resolution of 0.04 cm^?1. The frequencies of 600 lines were measured with an accuracy of ±0.003 cm^?1. Of these, approximately 368 are assigned as allowed transitions in ν₄, 95 are forbidden ν₄ transitions, and 137 belong to ν₂; maximum upper state J values are 20 for ν₄ and 19 for ν₂. The ground state tensor constants D_t, H_4t, and H_6t were obtained by fitting them to four rotational transitions observed by Kreiner and Opferkuch in the infrared-microwave double-resonance spectrum. An interacting-band analysis of the $\text{ν}{}_2\text{ν}{}_4$ diad then yields 22 spectroscopic constants for these Coriolis-coupled fundamentals and fits the experimental frequencies with an rms deviation of 0.0055 cm^?1 for 432 unblended lines that were assigned unit weight. A ν₄P⁺(12) transition at 943.3812 cm^?1, nearly coincident with the 10P(22) emission of the ¹²C¹⁶O₂ laser, has been investigated by heterodyne spectroscopy and its detuning (?64 MHz) and absorption coefficient have been determined. Such coincidences may lead to the development of laser analytical techniques for ¹³CD₄, which is a useful nonradioactive atmospheric tracer. ¹³CD₄ transitions that are within 300 MHz of isotopic CO₂ laser lines are tabulated for this purpose and for use in double-resonance experiments.     

The ground-state rotational constants of germane

The ground-state rotational constants B₀, D₀, and H₀ have been determined for GeH₄ from the analysis of ground-state combination differences in the infrared spectra of isotopically enriched ⁷⁰GeH₄, ⁷²GeH₄, and ⁷⁴GeH₄. The spectra were recorded at 0.06-cm^?1 resolution and about 0.005-cm^?1 precision for unblended lines. Suitable combination differences were found in both the ν₂ and the ν₄ infrared bands. The ground-state constants were assumed to be invariant to isotopic substitution at Ge, and the tensor distortion constants were held fixed at their microwave values. The results obtained are: B₀ = 2.69587 ± 0.00007 cm^?1, D₀ = (3.34 ± 0.03) × 10^?5 cm^?1, H₀ = (1.3 ± 0.5) × 10^?9 cm^?1.     

Crystal Structure of ϵ‐Ag7+xMg26–x – A Binary Alloy Phase of the Mackay Cluster Type

The binary alloy phase ϵ‐Ag_7+xMg_26–x with x ≈ 1 and small amounts of the β′‐AgMg phase crystallize by annealing of Ag–Mg alloys with starting compositions between 24–28 At‐% Ag at 390 to 420 °C. A model structure for the ϵ‐phase consisting of a fcc packing of Mackay clusters was derived from the known structure of the ϵ′‐Ag₁₇Mg₅₄ phase. Crystals of the ϵ‐phase were obtained by direct melting of the elements and annealing. The examination of a single crystal yielded a face‐centered cubic unit cell, space group Fm3 with a = 1761.2(5) pm. The refinement was started with the parameters of the model: wR2(all) = 0.0925 for 1093 symmetrically independent reflections. A refinement of the occupancy parameters indicated a partial replacement of silver for magnesium at two metal atom sites, resulting in the final composition ϵ‐Ag_7+xMg_26–x with x = 0.96(2). There are 264 atoms in the unit cell and the calculated density is 3.568 gcm^–3. The topology of the model was confirmed. Mackay icosahedra are located at the lattice points of a face‐centered cubic lattice. Differences between model and refined structure and their effects on the powder patterns are discussed. The new binary structure type of ϵ‐Ag_7+xMg_26–x can be described in terms of the I3‐cluster concept.     

The high-spin structure of 100Rh

High-spin states of ¹⁰⁰Rh have been populated with the reactions ⁹⁹Ru(α, 2np) and ⁹⁸Mo(⁶Li, 4n) and their γ-decay has been studied with Ge(Li) detectors in singles and coincidence. Angular and time distributions of the γ-rays were also measured. As a result 14 new levels spanning spins up to I = 16 built on the 5⁺, 4.5 min isomer at 107 keV have been established, and a half-life of $\text{T}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{= 120 ± 5}$ nsec has been determined for the 7⁺ state at 111.9 keV. The rotor-plus-two-quasiparticle model has been used to describe the observed level structure. The pn interaction is shown to be of negligible effect. On the other hand, the introduction of a soft core is essential. The application of the VMI model with the parameters extracted from the ⁹⁸Ru core yields a remarkably good agreement. This is the first time that the anomalous VMI root $\text{(}\text{I}{}_0\text{< 0)}$ has been applied to a doubly odd nucleus.     

Derivate von 4,5-dihydroxypyridonen durch ringerweiterung

The epimeric bromoghydrins 13/14 as well as their ethers 5/6 rearrange in the presence of silver ions to the 5-hydroxypyridones 15 or their ketals 9 respectively. with the bromohydrin ethers 5/6a and b this transformation is effected also with sodium methoxide. Under these reaction conditions the ring expansion is presumend ot proceed via bicyclic aziridines of which 7 could be issolated, The N-methylated compounds 5c/6c which cannot react likewise, form with sodium methoxide the 6-methoxypyridone 12 .